WO2016051750A1 - Revêtement à faible réflexion, plaque de verre, substrat de verre, et dispositif de conversion photoélectrique - Google Patents

Revêtement à faible réflexion, plaque de verre, substrat de verre, et dispositif de conversion photoélectrique Download PDF

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Publication number
WO2016051750A1
WO2016051750A1 PCT/JP2015/004893 JP2015004893W WO2016051750A1 WO 2016051750 A1 WO2016051750 A1 WO 2016051750A1 JP 2015004893 W JP2015004893 W JP 2015004893W WO 2016051750 A1 WO2016051750 A1 WO 2016051750A1
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reflection coating
low
substrate
low reflection
coating
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PCT/JP2015/004893
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English (en)
Japanese (ja)
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瑞穂 小用
河津　光宏
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日本板硝子株式会社
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Application filed by 日本板硝子株式会社 filed Critical 日本板硝子株式会社
Priority to MYPI2017701147A priority Critical patent/MY183225A/en
Priority to ES15845953T priority patent/ES2900831T3/es
Priority to US15/515,492 priority patent/US10600923B2/en
Priority to CN201580052163.7A priority patent/CN107076876B/zh
Priority to PL15845953T priority patent/PL3203273T3/pl
Priority to EP15845953.7A priority patent/EP3203273B1/fr
Priority to JP2016551529A priority patent/JP6771383B2/ja
Publication of WO2016051750A1 publication Critical patent/WO2016051750A1/fr
Priority to SA517381194A priority patent/SA517381194B1/ar

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/211—SnO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/213—SiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/24—Doped oxides
    • C03C2217/241—Doped oxides with halides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C03C2217/732—Anti-reflective coatings with specific characteristics made of a single layer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/90—Other aspects of coatings
    • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a low reflection coating, a glass plate on which the low reflection coating is formed, a glass substrate on which the low reflection coating is formed, and a photoelectric conversion device on which the low reflection coating is formed.
  • a low reflection coating is formed on the surface of a substrate such as glass or ceramic in order to transmit more light or prevent glare due to reflection for the purpose of improving the function of the substrate.
  • the low-reflection coating is formed on glass for vehicle, show window, or glass plate used for photoelectric conversion devices.
  • a so-called thin film solar cell which is a kind of photoelectric conversion device, uses a glass plate in which a photoelectric conversion layer and a back thin film electrode made of a base film, a transparent conductive film, amorphous silicon, and the like are sequentially stacked. Is formed on the main surface opposite to the main surface, that is, the main surface on the side where sunlight enters.
  • the solar cell in which the low reflection coating is formed on the sunlight incident side more sunlight is guided to the photoelectric conversion layer or the solar cell element, and the power generation amount is improved.
  • the most commonly used low-reflection coating is a dielectric film formed by vacuum deposition, sputtering, chemical vapor deposition (CVD), etc., but a fine particle-containing film containing fine particles such as silica fine particles should be used as the low-reflection coating.
  • the fine particle-containing film is formed by applying a coating liquid containing fine particles on a transparent substrate by dipping, flow coating, spraying, or the like.
  • Patent Document 1 a coating liquid containing fine particles and a binder precursor is applied to a glass plate having surface irregularities by a spray method, dried at 400 ° C., and then produced by a baking process at 610 ° C. for 8 minutes.
  • a cover glass for a photoelectric conversion device is disclosed.
  • the low reflection coating applied to the cover glass can improve the average transmittance of light having a wavelength of 380 to 1100 nm by at least 2.37%.
  • Patent Document 2 discloses a glass substrate coated by attaching a sol containing tetraethoxysilane, aluminum acetylacetonate, and colloidal silica to a glass plate by a dip coating method and performing a heat treatment at 680 ° C. for 180 seconds. It is disclosed.
  • the antireflection layer applied to the glass substrate can improve the average transmittance of light having a wavelength of 300 to 1100 nm by 2.5%.
  • Patent Document 3 discloses a coating composition containing colloidal silica, tetraalkoxysilane, and aluminum nitrate having a dispersed particle size larger than the average primary particle size and a shape factor and an aspect ratio of more than 1 to some extent, and a spin coater. There is disclosed a coated silicon substrate that is used and applied to a silicon substrate and dried by a drying process at 100 ° C. for 1 minute. Although the improvement of the average light transmittance by this coating is not described, this coating has a refractive index of 1.40 or less.
  • the transmittance gain is an increase in transmittance by applying a low-reflection coating with respect to transmittance, for example, average transmittance in a predetermined wavelength range. Specifically, it is obtained as a value obtained by subtracting that before applying the low reflection coating from the transmittance when the low reflection coating is applied to the substrate.
  • the low-reflection coating applied to the glass plate may be unintentionally damaged or soiled in the manufacturing process of the photoelectric conversion device, or the low-reflection characteristics may be deteriorated.
  • the photoelectric conversion device when actually used, the photoelectric conversion device is installed outdoors to allow sunlight to enter.
  • the photoelectric conversion device has a problem that dirt is attached due to rain or dust, and a part of incident light is blocked by the contamination, and output power of the photoelectric conversion device is reduced.
  • the problem associated with contamination of the low reflection coating may occur on a substrate on which the low reflection coating is formed other than the glass plate used in the photoelectric conversion device.
  • the present invention is suitable for being applied to a substrate that has not been subjected to a low-reflection coating, and in particular, a glass substrate that forms a surface on which light is incident on the photoelectric conversion device after the photoelectric conversion device is assembled.
  • An object of the present invention is to provide a low-reflective coating that is suitable for application to the surface and excellent in removing dirt caused by rain or dust.
  • the present invention A low reflection coating that can be applied to at least one of the major surfaces of the substrate,
  • the low-reflection coating has a film thickness of 80 to 800 nm, in which solid spherical silica fine particles having an average particle diameter of 80 to 600 nm are fixed by a binder containing silica as a main component and a hydrophobic group.
  • the transmittance gain obtained by applying the low reflection coating to the substrate is 1.5% or more, Provide a low reflection coating.
  • the transmittance gain is an increase in the average transmittance of the substrate having the low reflection coating with respect to the average transmittance of the substrate before the low reflection coating, with respect to the average transmittance in the wavelength region of 380 to 850 nm. It is.
  • the present invention also provides: Provided is a glass plate on which the low reflection coating is formed.
  • the present invention also provides: Provided is a glass substrate on which the low reflection coating is formed, wherein a transparent conductive film is formed on a main surface opposite to the main surface on which the low reflection coating is formed.
  • the present invention also provides: Having a glass plate, The low-reflection coating is formed on the main surface of the glass plate to which light is to be incident, A photoelectric conversion device is provided.
  • the low reflection coating has a high transmittance gain because it contains solid silica fine particles having an average particle diameter in a predetermined range and a binder containing silica as a main component at a predetermined content. Furthermore, since the binder of the low reflection coating contains a hydrophobic group at a predetermined content, the low reflection coating is excellent in the removal of attached dirt.
  • the low reflection coating of the present invention is a low reflection coating that can be applied to at least one of the substrates.
  • the low-reflection coating of the present invention is a porous film in which solid spherical silica fine particles are fixed by a binder mainly composed of silica.
  • “spherical” refers to a ratio (Dl / Ds) of the minimum particle diameter (Ds) to the maximum particle diameter (Dl) of 1.5 when the particles are observed with a scanning electron microscope (SEM). It means the following shape.
  • the binder includes a hydrophobic group.
  • the binder preferably further includes an aluminum compound.
  • the thickness of the porous film is, for example, 80 to 800 nm, preferably 100 to 500 nm, more preferably more than 100 nm and 150 nm or less.
  • the silica fine particles are spherical primary particles having an average particle size of, for example, 80 to 600 nm, preferably 100 to 500 nm, more preferably more than 100 nm and 150 nm or less. Since silica has a higher hardness than organic polymer materials and a relatively low refractive index, the apparent refractive index of a porous film composed of a binder and silica fine particles can be reduced. Furthermore, spherical primary particles having a uniform particle size made of silica are produced on a commercial scale at a low cost, and are easily available in terms of quantity, quality, and cost. In the present specification, the “average particle size” is determined by observing a cross section of the low reflection coating using a scanning electron microscope (SEM). Specifically, for any 50 particles that can observe the entire particle, the maximum and minimum diameters are measured and the average value is taken as the particle size of each particle, and the average value of the particle size of the 50 particles is “Average particle size”.
  • SEM scanning electron
  • the content of silica fine particles in the low reflection coating is, for example, 35 to 70% by mass.
  • the content of the silica fine particles in the low reflection coating is preferably 50 to 70% by mass, more preferably 55 to 65% by mass from one viewpoint. From another viewpoint, the content of the silica fine particles in the low reflection coating is preferably 35 to 55% by mass, and more preferably 40 to 55% by mass.
  • the content of silica contained in the binder in the low reflection coating is, for example, 25 to 64% by mass.
  • the content of silica contained in the binder is preferably 25 to 40% by mass, more preferably 28 to 38% by mass, from one viewpoint.
  • the content of silica contained in the binder is preferably 35 to 60% by mass, and more preferably 40 to 55% by mass.
  • silica means one constituted only by a silicon atom and an oxygen atom directly bonded to the silicon atom.
  • the content of hydrophobic groups in the low reflection coating is, for example, 0.2 to 10% by mass, preferably 0.5 to 8% by mass, and preferably 1 to 6% by mass, more preferably. Is 3 to 6% by mass.
  • the contact angle of water droplets in the low reflection coating can be increased to, for example, 70 ° or more, preferably 80 ° or more, more preferably 85 ° or more.
  • the low reflection coating has a high dirt removal property.
  • the content of the hydrophobic group in the binder is 1% by mass or more, the low reflection coating has high chemical durability.
  • the transmittance is an increment of the average transmittance of the substrate with the low-reflection coating with respect to the average transmittance of the substrate with the low-reflection coating.
  • the gain is, for example, 1.5% or more, preferably 2.0% or more, and more preferably 2.2% or more.
  • the transmittance gain is obtained by subtracting the average transmittance at 380 to 850 nm on the substrate not having the low reflection coating from the average transmittance at 380 to 850 nm on the substrate having the low reflection coating. In this case, light is incident on the low reflection coating of the substrate on which the low reflection coating is applied. Further, light is incident on the main surface of the substrate that is not provided with the low-reflection coating, on which the low-reflection coating is to be applied.
  • the hydrophobic group contained in the binder is derived from a hydrolyzable silicon compound or hydrolyzable silicon compound hydrolyzate having a hydrophobic group directly bonded to silicon, which is added to a coating solution for forming a low-reflection coating. It is preferable to do.
  • This hydrolyzable silicon compound includes, for example, a compound represented by the following formula (II).
  • Y that is a hydrolyzable group is preferably at least one selected from the group consisting of an alkoxyl group, an acetoxy group, an alkenyloxy group, an amino group, and a halogen atom.
  • R which is a hydrophobic group is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms in which at least a part of hydrogen atoms may be substituted with fluorine atoms, and more A chain alkyl group is preferable, a chain alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is particularly preferable.
  • the pseudo-stain formed by applying water in which the pseudo dust is suspended is applied to the substrate provided with the low reflection coating and dried. By rubbing, the pseudo-stain can be wiped away so that it cannot be recognized with the naked eye.
  • the ratio of the content of silica fine particles to the content of hydrolysis condensation products of hydrolyzable silicon compounds (content of silica fine particles: content of hydrolysis condensation products of hydrolyzable silicon compounds) )
  • mass ratio for example, in the range of 70:30 to 30:70, from one viewpoint, preferably 65:35 to 50:50, and from another viewpoint, preferably 60:40 It is in the range of 40:60.
  • the transmittance gain of the low reflection coating of the present invention can be increased as the content ratio of the silica fine particles increases. This is because a gap between the silica fine particles or between the silica fine particles and a substrate such as a transparent substrate becomes large.
  • silica fine particles when the content ratio of the silica fine particles exceeds the limit, the durability of the low reflection coating deteriorates.
  • Silica contained in the binder has a function of adhering between the silica fine particles or between the silica fine particles and a substrate such as a transparent substrate. However, if the content ratio of the silica fine particles is too large, the effect becomes poor. On the other hand, when the content ratio of the silica fine particles is smaller than the limit, the above-mentioned voids are too small, and the transmittance gain of the low reflection coating is lowered.
  • the aluminum compound is preferably derived from a water-soluble inorganic aluminum compound added to the coating solution for forming the low reflection coating, such as aluminum halide or aluminum nitrate. More preferably derived.
  • the preferred aluminum halide is aluminum chloride.
  • the content of the aluminum compound in the low reflection coating is, for example, 2 to 7% by mass, preferably 4 to 7% by mass, when the aluminum compound is converted to Al 2 O 3 .
  • the chemical durability of the low reflection coating is improved.
  • the aluminum compound content is less than 2% by mass, the chemical durability of the low-reflective coating decreases, whereas when the aluminum compound content exceeds 7% by mass, the transmittance gain of the low-reflective coating decreases. .
  • the low reflection coating may contain other additives.
  • the other additive include a titanium compound and a zirconium compound.
  • durability of the low reflection coating with respect to alkali can be improved.
  • the low reflection coating may contain a phosphorus compound in terms of P 2 O 5 in an amount of 0.1 to 5% by mass.
  • the silica contained in the binder is derived from, for example, a hydrolyzable silicon compound or a hydrolyzate of a hydrolyzable silicon compound added to a low reflection coating solution for forming a low reflection coating.
  • This hydrolyzable silicon compound includes, for example, a compound represented by the following formula (I).
  • X is at least one selected from the group consisting of an alkoxyl group, an acetoxy group, an alkenyloxy group, an amino group, and a halogen atom.
  • the hydrolyzable silicon compound includes an oligomer of the hydrolyzable silicon compound.
  • This oligomer is formed, for example, by condensing about 2 to 200 molecules of the same type.
  • a hydrolyzable silicon compound typified by silicon alkoxide can be used as a supply source of silica contained in the binder.
  • the silicon alkoxide include tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane.
  • These hydrolyzable silicon compounds are hydrolyzed and polycondensed by a so-called sol-gel method to constitute a binder.
  • Hydrolysis of the hydrolyzable silicon compound can be carried out as appropriate, but is preferably carried out in a solution containing silica fine particles.
  • the silicon alkoxide may be a monomer or an oligomer.
  • an acid and a base can be used for a hydrolysis catalyst, it is preferable to use an acid, especially an acid with a large degree of ionization in aqueous solution. Specifically, it is preferable to use an acid having an acid dissociation constant pKa (meaning a first acid dissociation constant when the acid is a polybasic acid) of 2.5 or less.
  • pKa meaning a first acid dissociation constant when the acid is a polybasic acid
  • suitable acids include volatile inorganic acids such as hydrochloric acid and nitric acid, organic acids such as trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid, and maleic acid, phosphoric acid, and Mention may be made of polybasic acids such as oxalic acid.
  • the acidity is basic, the dispersibility of the silica fine particles is better, and the stability of the coating liquid is also better.
  • chloride ions derived from hydrochloric acid increase the concentration of chloride ions in the coating solution, and thus promote the effect of aluminum chloride added to the coating solution described above.
  • the transmittance gain can be increased to, for example, 1.5% or more, preferably 2.5% or more, more preferably 2.6% or more, and the above-described excellent Show chemical durability.
  • the silica fine particles are contained in an amount of 35 to 55% by mass and the silica contained in the binder is contained in an amount of 35 to 60% by mass
  • the absolute value of the difference between the average transmittance of light with a wavelength of 380 to 850 nm and the average transmittance of light with a wavelength of 380 to 850 nm on a substrate with a low reflection coating before the chemical durability test is performed. For example, it is 0.25% or less.
  • the chemical endurance test conforms to JIS (Japanese Industrial Standards) C8917: 2005 appendix 4 by spraying a low-reflection coating with a 5% by mass sodium chloride aqueous solution having a temperature of 35 ° C. for 192 hours.
  • JIS Japanese Industrial Standards
  • the average transmittance of light having a wavelength of 380 to 850 nm is an arithmetic average of the transmittance of light having a wavelength of 380 to 850 nm.
  • the low reflection coating has a high chemical durability in some cases.
  • the reflectance loss after the reciprocating wear test obtained as follows is, for example, 1 0.6% or more, preferably 2.0% or more.
  • the reflectance loss after the reciprocating wear test is determined by reciprocating wear by bringing the wearer CS-10F into contact with the low-reflective coating from the average reflectivity of light having a wavelength in the range of 360 to 740 nm on the substrate not subjected to the low-reflective coating.
  • the low reflection coating has high wear resistance in some cases in addition to high chemical durability.
  • the low reflection coating of the present invention can be formed, for example, by applying, drying and curing a coating solution.
  • a coating solution any known method such as spin coating, roll coating, bar coating, dip coating, spray coating, etc. can be used, but spray coating is excellent in terms of mass productivity, Roll coating or bar coating is more suitable in terms of the homogeneity of the appearance of the low reflection coating in addition to mass productivity.
  • the low-reflection coating preferably has a maximum substrate temperature of 200 ° C. or more and 350 ° C. or less after the coating liquid for forming the low-reflection coating is applied to the substrate, and the substrate temperature is 200 ° C. or more. It is formed by being heated so that a certain time is 5 minutes or less. More preferably, the low-reflection coating has a maximum substrate temperature of 120 ° C. or more and 250 ° C. or less after the coating liquid for forming the low-reflection coating is applied to the substrate, and the substrate temperature is 120 ° C. It is formed by heating so that the above time is 3 minutes or less. More preferably, the low reflection coating has a maximum temperature of 100 ° C. or more and 250 ° C.
  • the low reflection coating of the present invention can be formed by heating at a relatively low temperature in some cases.
  • the low reflection coating can be dried and cured, for example, by hot air drying.
  • the substrate to which the low reflection coating of the present invention can be suitably applied may be a glass plate that is not coated. That is, according to the present invention, it is possible to obtain a glass plate on which the low reflection coating is formed.
  • the glass plate may be a float plate glass having a smoothness with an arithmetic average roughness Ra of the main surface of, for example, 1 nm or less, preferably 0.5 nm or less.
  • the arithmetic average roughness Ra is a value defined in JIS B0601-1994.
  • the glass plate may be a template glass having irregularities on its surface, and the average interval Sm of the irregularities is, for example, 0.3 mm or more, preferably 0.4 mm or more, more preferably 0.45 mm or more. And, for example, 2.5 mm or less, preferably 2.1 mm or less, more preferably 2.0 mm or less, and particularly preferably 1.5 mm or less.
  • the average interval Sm means the average value of the intervals of one mountain and valley obtained from the point where the roughness curve intersects the average line.
  • the unevenness on the surface of the template glass plate preferably has a maximum height Ry of 0.5 ⁇ m to 10 ⁇ m, particularly 1 ⁇ m to 8 ⁇ m, together with the average interval Sm in the above range.
  • the average interval Sm and the maximum height Ry are values defined in JIS B0601-1994.
  • a glass plate may be the same composition as normal plate glass and building plate glass, it is preferable that a coloring component is not included as much as possible.
  • the content of iron oxide which is a typical coloring component, is preferably 0.06% by mass or less, particularly preferably 0.02% by mass or less in terms of Fe 2 O 3 .
  • the substrate to which the low reflection coating of the present invention can be suitably applied may be a glass substrate with a transparent conductive film.
  • This glass substrate with a transparent conductive film has a transparent conductive film on one main surface of any of the glass plates described above, for example, and has one or more underlayers such as fluorine on the main surface of the glass plate.
  • a transparent conductive layer mainly composed of doped tin oxide is sequentially laminated. In this case, the transparent conductive film is formed on the main surface opposite to the main surface on which the low reflection coating of the glass plate is formed.
  • the low reflection coating is preferably formed on the bottom surface of the glass plate, which is the main surface formed by the glass that was in contact with the molten tin in the float bath.
  • the transparent conductive film is preferably formed on the top surface of the glass plate, which is the main surface formed of glass that has not touched the molten tin in the float bath.
  • the transparent conductive film is formed on the main surface opposite to the main surface on which the low reflection coating is formed, on the glass substrate on which the low reflection coating is formed. A glass substrate can be obtained.
  • a photoelectric conversion device having a glass plate and having the low reflection coating formed on the main surface of the glass plate on which light should be incident can be obtained.
  • the dirt removal property is determined by visually observing whether or not the pseudo-stain can be wiped off after rubbing the specified pseudo-stain formed on the surface of the low-reflective coating with a dry cloth, and whether or not the low-reflective coating is scratched. Was observed using an optical microscope at a magnification of 100 times.
  • the pseudo soil was formed by applying water in which predetermined pseudo dust was suspended and drying.
  • the seventh type “Kanto Loam” manufactured by Japan Powder Industrial Technology Association
  • Suspended water was obtained by suspending pseudo dust in water four times its mass.
  • the pseudo-stain was formed by dropping 0.5 ml of the suspended water onto a test object held horizontally and leaving it in the atmosphere for 16 hours.
  • Table 1 The results regarding each example and each comparative example are shown in Table 1.
  • Contact angle As for the contact angle, about 4 ⁇ L of water droplets were dropped on the surface using a contact angle meter (model: CA-A) manufactured by Kyowa Interface Science Co., Ltd., or the low reflection coating according to Example or Comparative Example 2 or the glass of Comparative Example 1 The contact angle of the water droplet on the surface of the substrate was measured. The results regarding each example and each comparative example are shown in Table 1.
  • a reciprocating wear test was performed on the substrates on which the low reflection coatings according to Examples 4 to 11 and Comparative Example 2 were formed using a reciprocating wear tester manufactured by Daiei Kagaku Seiki Seisakusho. Specifically, the substrate on which the low reflection coating was formed was fixed with a jig with the low reflection coating side facing upward. Next, a circular surface of a disc-shaped wear piece CS-10F having a diameter of 19 mm was brought into contact with the low reflection coating, and a load of 4N was applied. At this time, the contact area between the wear piece CS-10F and the low reflection coating was 284 mm 2 . In this state, the wearer CS-10F was reciprocated linearly 50 times with respect to the low reflection coating. The speed of the wearer at this time was set to 120 mm / second, and the stroke width of the wearer was set to 120 mm.
  • the average reflectance of the substrate on which the low reflection coating according to Examples 4 to 11 and Comparative Example 2 was formed was also determined in the same manner for the substrate before the low reflection coating was formed.
  • reciprocal wear is obtained by subtracting the average reflectivity of the substrate on which the low-reflection coating before performing the reciprocal wear test from the average reflectivity of the substrate before forming the low-reflective coating.
  • the reflectance loss before the test was determined.
  • the round trip was performed by subtracting the average reflectance of the substrate on which the low-reflection coating was formed after performing the round-trip wear test from the average reflectance of the substrate before forming the low-reflection coating.
  • the reflectance loss after the wear test was determined. The light for measuring the reflectance was made incident on the surface of the substrate on which the low reflection coating or the low reflection coating is to be formed. The results are shown in Table 1.
  • an average transmittance of light having a wavelength of 380 to 850 nm on a substrate on which a low-reflection coating was formed was obtained using a spectrophotometer (UV-3100PC, manufactured by Shimadzu Corporation). It was. Thereafter, the average transmittance of light having a wavelength of 380 to 850 nm after the salt spray test and the substrate with the low reflection coating before the salt spray test are performed. The absolute value of the difference from the average transmittance of light having a wavelength of 380 to 850 nm was calculated. The results are shown in Table 1.
  • the low reflection coating according to each example and each comparative example was observed using a field emission scanning electron microscope (FE-SEM) (manufactured by Hitachi, Ltd., model: S-4500). From the FE-SEM photograph of the cross section of the low-reflection coating obliquely from 30 ° above, the average value of the thickness of the low-reflection coating at five measurement points was calculated as the film thickness (average film thickness) of the low-reflection coating. An FE-SEM photograph of the glass plate with low reflection coating according to Example 4 is shown in FIG.
  • FE-SEM field emission scanning electron microscope
  • Example 1> (Preparation of coating solution) Silica fine particle dispersion (Quatron PL-7, substantially spherical primary particles having an average particle diameter of 125 nm, solid content concentration 23 wt%, manufactured by Fuso Chemical Industries Ltd.) 56.2 parts by mass, 1-methoxy-2-propanol (solvent ) 23.3 parts by mass, 1 part by mass of 1N hydrochloric acid (hydrolysis catalyst) is stirred and mixed, and further stirred, tetraethoxysilane (normal ethyl silicate, manufactured by Tama Chemical Co., Ltd.) 12.1 parts by mass, methyltriethoxy 7.1 parts by mass of silane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was stirred for 8 hours while keeping the temperature at 40 ° C.
  • tetraethoxysilane normal ethyl silicate, manufactured by Tama Chemical Co., Ltd.
  • the ratio of the mass of the silica fine particles to the mass of the hydrolytic condensation product of the hydrolyzable silicon compound contained in the binder is 67.7: 32.3, and the hydrolysis of the hydrolyzable silicon compound
  • the hydrolysis condensation product of the hydrolyzable silicon compound having a hydrophobic group with respect to 100 parts by mass of the condensation product was 43.4 parts by mass.
  • coating liquid A1 52.5 g of the above-mentioned stock solution A, 3.0 g of propylene glycol (solvent), 92.0 g of 1-methoxy-2-propanol (solvent), an aqueous solution of aluminum chloride (concentration 47.6 wt% as AlCl 3 , reagent grade aluminum chloride 6 water) 2.49 g (prepared by dissolving a Japanese product (manufactured by Sigma Aldrich) in deionized water) was stirred and mixed to obtain coating liquid A1.
  • coating liquid A1 the solid content concentration of silica (derived from silica fine particles and alkoxysilane) converted to SiO 2 is 7.0% by mass, and the silicon oxide converted to SiO 2 is 100 parts by mass.
  • the aluminum compound converted to Al 2 O 3 was 5 parts by mass, and the hydrophobic group content in the solid content of the coating liquid A1 was 2.8% by mass.
  • a low reflection coating was formed on the main surface of the glass plate with a transparent conductive film on which the transparent conductive film was not formed.
  • This glass plate with a transparent conductive film has a thickness of 3.2 mm, in which a transparent conductive film including a transparent conductive layer is formed on one main surface of a glass plate having a normal soda lime silicate composition using an on-line CVD method. It was a glass plate manufactured by Nippon Sheet Glass Co., Ltd. Since this glass plate has a transparent conductive film formed by an on-line CVD method, the glass plate to which the transparent conductive film is deposited was a glass plate formed by a float method.
  • the transparent conductive film was formed in the top surface which is the main surface of the glass plate formed with the glass which was not touching molten tin in the float bath.
  • This glass plate with a transparent conductive film is cut into 200 mm ⁇ 300 mm, immersed in an alkaline solution (alkaline cleaning solution LBC-1, manufactured by Reybold Co., Ltd.), then cleaned using an ultrasonic cleaner, and further washed with deionized water. And then dried at room temperature. In this way, a glass plate (substrate) for forming a low reflection coating was produced.
  • the average transmittance was 80.0%.
  • the coating liquid A1 was applied to the main surface of the glass plate on which the transparent conductive film was not applied. At this time, the thickness of the coating solution was adjusted to 1 to 5 ⁇ m.
  • the coating liquid applied to the glass plate was dried and cured with hot air.
  • This hot air drying uses a belt-conveying hot air drying device, the hot air set temperature is set to 300 ° C., the distance between the hot air discharge nozzle and the glass plate is set to 5 mm, and the conveying speed is set to 0.5 m / min. This was performed by reciprocating four times and passing under the nozzle four times.
  • the time during which the glass plate coated with the coating solution was in contact with hot air was 140 seconds, and the maximum temperature reached on the glass surface coated with the coating solution of the glass plate was 199 ° C. Moreover, the time when the temperature of the glass surface on which the coating solution for the glass plate was applied was 120 ° C. or more was 125 seconds.
  • the glass plate after drying and curing was allowed to cool to room temperature, and a low reflection coating was applied to the glass plate.
  • the low reflection coating was formed on the bottom surface, which is the main surface of the glass plate formed of the glass that had been in contact with the molten tin in the float bath.
  • Example 2> Preparation of coating solution 28.3 parts by mass of the silica fine particle dispersion used in Example 1, 58.6 parts by mass of 1-methoxy-2-propanol (solvent), and 1 part by mass of 1N hydrochloric acid (hydrolysis catalyst) were mixed and stirred. While adding 12.1 parts by weight of tetraethoxysilane (normal ethyl silicate, manufactured by Tama Chemical Industry Co., Ltd.), the mixture was stirred for 8 hours while being kept at 40 ° C. to hydrolyze tetraethoxysilane to obtain a stock solution B. .
  • tetraethoxysilane normal ethyl silicate, manufactured by Tama Chemical Industry Co., Ltd.
  • stock B a mass obtained by converting the silica fine particles to the SiO 2, the ratio of the mass obtained by converting the silicon oxide component contained in the binder SiO 2 is 65: A 35, solid concentration in terms of SiO 2 is 10 mass %Met.
  • Stock solution B did not contain any hydrophobic groups.
  • Comparative Example 1 As Comparative Example 1, the glass plate with a transparent conductive film used in Examples 1 and 2 was used without applying a low reflection coating on the main surface on which the transparent conductive film was not formed. Prior to evaluation, it was washed and dried in the same manner as in Examples 1 and 2. The evaluation results are shown in Table 1.
  • the low reflection coating only by curing by hot air drying showed an extremely high transmittance gain of 2.5% or more and excellent dirt removal property. Furthermore, in the low reflection coating of Example 2, excellent scratch resistance comparable to that of the glass substrate surface before coating was obtained.
  • Example 4 Silica fine particle dispersion (Quartron PL-7, substantially spherical primary particles having an average particle size of 125 nm, solid content concentration 23% by weight, manufactured by Fuso Chemical Industry Co., Ltd.) 21.7 parts by mass, 1-methoxy-2-propanol (solvent ) 64.5 parts by mass, 1 part by mass of 1N hydrochloric acid (hydrolysis catalyst) was stirred and mixed, and further the partial hydrolysis condensate of tetraethoxysilane (manufactured by Colcoat Co., Ltd., trade name: ethyl silicate 40, abbreviation: ES-40, oligomer of average pentamer) 7.7 parts by mass, and 5.1 parts by mass of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were added, followed by stirring for 8 hours while keeping the temperature at 40 ° C. ES-40 and methyltriethoxysi
  • a low reflection coating was applied to the glass plate in the same manner as in Example 1 except that the coating liquid C1 was used instead of the coating liquid A1, and the above-mentioned characteristics were evaluated.
  • the content of each component in the low reflection coating formed from the coating liquid C1 was as follows. Silica fine particles 47.1% by mass Silica contained in binder 43.0% by mass Hydrophobic group 4.0% by mass Aluminum compound converted to Al 2 O 3 5.9% by mass
  • the ratio between the content of the silica fine particles and the content of the hydrolytic condensation product of the hydrolyzable silicon compound was 50:50 in mass ratio. It was.
  • Examples 3, 5 to 8> In addition to adjusting the addition amount of each raw material so that the content of the aluminum fine particle converted into silica fine particles, binder, silica, hydrophobic group, and Al 2 O 3 in the low reflection coating is as shown in Table 1.
  • the solid content in the coating solutions according to Examples 3 and 5 to 8 was 7% by mass.
  • glass plates with low-reflection coating according to Examples 3 and 5 to 8 were produced in the same manner as Example 1, except that the coating liquid according to Examples 3 and 5 to 8 was used instead of the coating liquid A1. did.
  • Example 9 > 26.1 parts by mass of the silica fine particle dispersion used in Example 1, 58.7 parts by mass of 1-methoxy-2-propanol (solvent), phosphoric acid aqueous solution (phosphoric acid (manufactured by Tokyo Chemical Industry Co., Ltd., concentration 89 mass) %) Is dissolved in deionized water to prepare a 9.0% by mass aqueous solution) 5.0 parts by mass with stirring, and 6.2 parts by mass of the aforementioned ES-40 and methyltril with stirring. 4.0 parts by mass of ethoxysilane was added to obtain a stock solution D.
  • a coating solution D1 was obtained in the same manner as in Example 4 except that the stock solution D was used instead of the stock solution C.
  • the glass plate was subjected to low reflection coating in the same manner as in Example 1 except that the coating solution D1 was used instead of the coating solution A1, and a glass plate with low reflection coating according to Example 9 was produced.
  • Example 10 The amount of 1-methoxy-2-propanol (solvent) added was changed to 62.7 parts by mass, and instead of phosphoric acid aqueous solution, 10 g of trifluoroacetic acid aqueous solution (trifluoroacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) Prepared by dissolving in water)
  • a stock solution E was obtained in the same manner as in Example 9 except that 1.0 part by mass was used.
  • a coating solution E1 was obtained in the same manner as in Example 4 except that the stock solution E was used instead of the stock solution C.
  • a glass plate with a low reflection coating according to Example 10 was produced by applying a low reflection coating to the glass plate in the same manner as in Example 1 except that the coating liquid E1 was used instead of the coating liquid A1.
  • Example 11 Oxalic acid aqueous solution instead of trifluoroacetic acid aqueous solution (prepared by dissolving 10 g of oxalic acid dihydrate (manufactured by Kanto Chemical Co., Ltd.) in 90 g of deionized water, oxalic acid concentration: 7.1 mass%)
  • a stock solution F was obtained in the same manner as in Example 10 except that 0 part by mass was used.
  • a coating F1 was obtained in the same manner as in Example 4 except that the stock solution F was used instead of the stock solution C.
  • the glass plate was subjected to low reflection coating in the same manner as in Example 1 except that the coating solution F1 was used instead of the coating solution A1, and a glass plate with low reflection coating according to Example 11 was produced.
  • ⁇ Comparative example 2> The same as Example 4 except that methyltriethoxysilane was not used and the amount of each raw material was adjusted so that the content of each component in the solid content of the coating liquid according to Comparative Example 2 was as shown in Table 1. Thus, a coating solution according to Comparative Example 2 was prepared. In addition, the density
  • the contact angle in the low reflection coating according to Comparative Example 2 was 6.6 °
  • the contact angle in the low reflection coating according to Examples 3 to 11 was 79.8 ° or more. there were.
  • the transmittance gains in the low reflection coatings according to Examples 3 to 8 were 2.24 or more, indicating a relatively high transmittance gain.
  • the reflectance loss after the reciprocating wear test in the low reflection coating according to Examples 4 to 8 is 1.55 while the reflectance loss after the reciprocating wear test in Examples 4 to 8 is 2. It was 33 or more. For this reason, it was shown that the low reflection coatings according to Examples 4 to 8 have good wear resistance.
  • the absolute value of the difference in average transmittance before and after the salt spray test in the low reflection coating according to Comparative Example 2 is 0.27, whereas before and after the salt spray test in the low reflection coating according to Examples 4 and 5.
  • the absolute values of the difference in average transmittance were 0.11 and 0.20, respectively. For this reason, it was shown that the low-reflection coating according to Examples 4 and 5 has good chemical durability.

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Abstract

L'invention concerne un revêtement à faible réflexion, qui peut être appliqué sur au moins une surface principale d'un substrat. Ce revêtement à faible réflexion est un film poreux qui est obtenu par fixation de particules de silice fines sphériques solides ayant un diamètre moyen de particule de 80-600 nm au moyen d'un liant qui contient un groupe hydrophobe, tout en contenant de la silice comme constituant principal, et qui a une épaisseur de film de 80-800 nm. En outre, ce revêtement à faible réflexion contient, en % en masse, 35-70 % de particules de silice fines, 25-64 % de silice contenue dans le liant, et 0,2-10 % du groupe hydrophobe dans le liant. Le gain de facteur de transmission, obtenu par application de ce revêtement à faible réflexion sur un substrat, est de 1,5 % ou plus.
PCT/JP2015/004893 2014-09-30 2015-09-25 Revêtement à faible réflexion, plaque de verre, substrat de verre, et dispositif de conversion photoélectrique WO2016051750A1 (fr)

Priority Applications (8)

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MYPI2017701147A MY183225A (en) 2014-09-30 2015-09-25 Low-reflection coating, glass sheet, glass substrate, and photoelectric conversion device
ES15845953T ES2900831T3 (es) 2014-09-30 2015-09-25 Placa de vidrio revestida de baja reflexión, sustrato de vidrio y dispositivo de conversión fotoeléctrica
US15/515,492 US10600923B2 (en) 2014-09-30 2015-09-25 Low-reflection coating, glass sheet, glass substrate, and photoelectric conversion device
CN201580052163.7A CN107076876B (zh) 2014-09-30 2015-09-25 低反射涂层、玻璃板、玻璃基板、以及光电转换装置
PL15845953T PL3203273T3 (pl) 2014-09-30 2015-09-25 Płyta szklana powleczona nisko-odblaskowo, podłoże szklane oraz urządzenie do konwersji fotoelektrycznej
EP15845953.7A EP3203273B1 (fr) 2014-09-30 2015-09-25 Plaque de verre avec revêtement à faible réflexion, substrat de verre, et dispositif de conversion photoélectrique
JP2016551529A JP6771383B2 (ja) 2014-09-30 2015-09-25 低反射コーティング、低反射コーティングを製造する方法、ガラス板、ガラス基板、及び光電変換装置
SA517381194A SA517381194B1 (ar) 2014-09-30 2017-03-26 طلاء منخفض الإنعكاس

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WO2018198937A1 (fr) * 2017-04-27 2018-11-01 日本板硝子株式会社 Substrat transparent revêtu de film de revêtement, liquide de revêtement pour former un film de revêtement pour substrat transparent revêtu de film de revêtement, et procédé de production pour substrat transparent revêtu de film de revêtement
WO2018198936A1 (fr) * 2017-04-27 2018-11-01 日本板硝子株式会社 Substrat transparent revêtu d'un film à faible réflexion, dispositif de conversion photoélectrique, liquide de revêtement pour former un film à faible réflexion pour substrat transparent revêtu d'un film à faible réflexion, et procédé de production pour substrat transparent revêtu d'un film à faible réflexion
CN109791221A (zh) * 2016-07-28 2019-05-21 日本板硝子株式会社 带低反射涂层的玻璃板、制造带低反射涂层的基材的方法及用于形成带低反射涂层的涂敷液
JP2019139208A (ja) * 2018-02-13 2019-08-22 日本板硝子株式会社 膜、液状組成物、光学素子、及び撮像装置
JP2020518684A (ja) * 2017-04-18 2020-06-25 ディーエスエム アイピー アセッツ ビー．ブイ．Ｄｓｍ Ｉｐ Ａｓｓｅｔｓ Ｂ．Ｖ． コーティング及びコーティング配合物
WO2023026670A1 (fr) * 2021-08-23 2023-03-02 フクビ化学工業株式会社 Verre antireflet
US12006439B2 (en) 2019-03-27 2024-06-11 Canon Kabushiki Kaisha Optical member, optical device and coating liquid

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CN108732655B (zh) * 2017-04-17 2020-06-30 法国圣戈班玻璃公司 光学组件及制造方法，光伏器件
US11118070B2 (en) 2018-12-21 2021-09-14 Eastman Kodak Company Low specular reflectance surface
US10793727B2 (en) 2018-12-21 2020-10-06 Eastman Kodak Company Matte paint composition

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MY183225A (en) 2021-02-18
EP3203273B1 (fr) 2021-11-17
US20170243989A1 (en) 2017-08-24
TW201625986A (zh) 2016-07-16
CN107076876A (zh) 2017-08-18
JP6771383B2 (ja) 2020-10-21
CN107076876B (zh) 2019-05-07
SA517381194B1 (ar) 2021-03-15
EP3203273A1 (fr) 2017-08-09
US10600923B2 (en) 2020-03-24
ES2900831T3 (es) 2022-03-18
TWI701456B (zh) 2020-08-11
JPWO2016051750A1 (ja) 2017-08-31
JP6989650B2 (ja) 2022-01-05

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